Estil hatrsboreer



i Patented Fb. 1o, a v

' l 1mm 4 V or new YORK, N. 2., a oonroqaamronflor DELAWARE j V g PROCESS OFPREPARING rsArriTAnD DEBIIVATIVESEHEREOE IN o Application filed 2 2, 192 9Qserla1 NoPSjQSflGG, and inGerma'ny t I The; present invention relates to a'15rocess I vof preparing isatin and derlvatlves'thereo l y We have found that cyanoiorniarylides or" t e f llowing general formula; '7 I g V g Y g and dr ed. 1

- 7 wherein H stands for asnbstituted or u'nsuh;

' stituted aromatic residue having atleast one freeortho-position to the imin j'grou may "be; transformed into isatins by ring-closure with a condensing metal chloride as 'f rin- .stance aluminium chloride, zinc chloride or the like. The reaction may be illustrated by the following equationj "sodium; chloride While heating to a temperisatins are obtained almost in all cases with an excellent yield.

trate our invention but they are notintended tolimit it thereto, the parts bemg by weight. (1) 120 parts of aluminium'chlorlde and 30 parts of sodium chloride are melted. At t r a temperature of from 100 CL'tOlIO C'. 30

iormu1a:

arts of cyanoformanilide of the following i I ONE-OO-TJN and having point at 120"v C.

poured on ice and Water to which diluted hydrochloric has been added, heated ,The following examples serve to illus-x for al short um andjthu again allowed to l t cool. The isatin which has separatedl in the form of orangeredlflakes is filtered by'suction, washed with 'll (2)1120 'partsfof aluminium chloride and sac-parts ofcyanbformanilide are introducedf intofl parts ottrichlorbenzena The'i'ni M .t'u-reis heated-Whilestirring, At'afit'emperature of-t'roin 50- CitoSO" C. the coloration? ,7 o the 'melt 'turnsf aarkamwm e Tea-0:

GEORG KRKNZLEIN, ARTHUR WOLFE/AM", ano nt/rmfnnusnolannm or' rnanfironrra O1\T4THE-MAIN' HOCHST, GERM NY,- ssrenoas 1T0 GENEnAn-ummnnwouxs,1n

i qu entity-of water i tion does not proceed so quickly as in EX- ample 1; The temperaturelraised to170" tion is filtered"; on "cooling it the; isatin c-rystallizes out from the solution. r

(5): parts "of 'aluminium chloride and I v g 2O partsof sodium chloride are'fused together There action Ilreferably carried out in the presence ofa'diluent or a melting agent 'asfor instance nitrobenzene, trichlorbenzeneor and then 19'p'arts of cyanoform- (2-m'eth yl- 3- chlor)-anilide of the following formula:

m ma a rl gi uoe gol t5 108 -0.ffihii15 frothing) are gradually introduced at'from 1 0091C to (lf 'while stirringV- During. the operation'the temperature rises up to C. After about 5 minutes the formation of isatin is complete. I The melt is given on ice, the acidifieclliquoris heated for a short time, the i'satin which has separated in the 1 form of orange flakes isfiltered ofl' byws'uc- .v tion, wa hedwith w ter and d ied; wPrac ,ti'c ally, pure 6ehlor fZ methylisatiu is .ob-

taine'df{iAfter-irecrystallizationjfromglacial acetic acid, the' is n; melts at :from; 245 O.

anilide) of the lollowii'igformula v -of 80 parts of aluminium chloride and 20 parts of sodium ,chloride',flwhile. stirring;

The temperature rises up to-120 O. After to Example 3.* The 4 6-dichlorisatin-is'fob talliz ation; fromglacial -ace tic-xacic1; it 3 melts c -f thylamine of the foll'owing formulai; c I

melting atfrom 143 ually introduced"at about from' 100 to 10 5 C. into the melt of parts of aluminium l r e and: 20.- r attsuef sodium h o' d h e tir i h tem eii ture is wed to rise to 1110 After a few minutes the Yformation of isatin isc omplete. The melt l is. worked up according to Example 8.. The

2.1-naphthisatin is obtainedin the .formfofa dark-redproduct. It is purified by way 0t thebisulfite compound and then forms smallred needles of themelting'point 248? C. I

(6) 80 parts of aluminium-chloride and 20 parts of sodium chloride "are fused to gether and then20'p arts of cyanoform-(3.5- dimethyl) -anilide of the followingformula:

naphthylamine) of the renewing formula NH-O O-ON injtli'e'fcours'e of about L20 minutes iiito a melt rQ parts" of alummimn chloride" and 20 art of odium ands-a6; while (stirring;

Stirring" iscontinuedfor' about 10 us '15 min; utes and-the. melt is poured on ice; After re crystallizationflthe' I-chIofoZi3 naphtliisatin I thus obtained melts zit 262 C."

We claim: c c lhThe process which comprises heating a compound of the following formula:

RNHCOCN wherein R stands for substituted or unsubstituted aromatic residue havingat least one unsubstitut edposi tion ortho to the. imino diluent. f

h ed: sodium and aluminium 111 V rides. v V

group, with a con-Q densingmetal chloride. V V

2. The process 'which comprises heating a compound of the following; formula; R .NH 1 CD CN wherein -'R-"stantls for a substituted or unsubstituted areuiati'e residue-having at least. one unsubstituted p'osi- 'v v ed h en 6 .1 yiel Aft rrePy%;; i

; s isinee e e i l de;- i1 -t e p esen of tion iortho to' the imin o=g1oup -with ameni 3 The i process wliich comprises: heating at; arternperature ofiv betweem- "CL and i g 140 on v m'ulsiiy} compound of the following for wherein stands for hydrogen andwherein f the othernuclear hydrogen atoms may be with a condensing metal chloride.

wherein Xfstands for hydrogen and'wherein the other-nuclear hydrogen atoms may be substituted or notfby' any uniyalent residhe 10s 5. The process which comprises heating at a ,temperature of' between- 60 ]G, and? 140 C. a compound-ofthe followingrfor mular 4 V wherein; Xi standsifor hydrogen o'ralkylg and X5 for hydi'bgen, halogen oi' alk'yl, with a condensing metal chloride.

at a temperature ofbetween"60 '.cj 140? C. 'a compound of the following 'for mula:

6. The process wlncli" comprises lratmgi at temperature of'b'etwe'eri 66 o. and? 1 i l 150 C. cyanoformanilide with'acondensing metal'chloi ide. V p I p p h p ocess which icomprises heating 1 9 1 p ii at a temperature of between 100 G.- and: 110C. cyanoformanilide with melted so dium and aluminium chlorides;

'9. The process which comprises heating. a compound of the following formula:

R -NH-GO GN wherein R stands for a '10 substituted or unsubstituted aromatic i'esiei due having atflleastone unsubstituted position ortho to theimino group, with melted I alkali metal and aluminium chlorides; v

10. Thep rocess which comprises heating 7 a compound of the following formula:

R-NHCOGN wherein R stands for. a

V hsubstituted or unsubstituted aromatic .residue having at leastone unsubstituted posiition ortho to the imino-group, with melted :2 'alkalimetaland aluminium chloridesin the 1 presence of a diluent. L I

In testimony whereof we afiix our signatures.

GEORG :KRLK'NZLEIN.

p 7 ART URjWoLFR M, J

VEMIL HAU DORF 

